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EP1387859B1 - Dispersions de polyurethanne-polyuree utilisees comme agent d'enduction - Google Patents

Dispersions de polyurethanne-polyuree utilisees comme agent d'enduction Download PDF

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Publication number
EP1387859B1
EP1387859B1 EP02730221A EP02730221A EP1387859B1 EP 1387859 B1 EP1387859 B1 EP 1387859B1 EP 02730221 A EP02730221 A EP 02730221A EP 02730221 A EP02730221 A EP 02730221A EP 1387859 B1 EP1387859 B1 EP 1387859B1
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EP
European Patent Office
Prior art keywords
polyols
dispersions according
polycarbonate
polytetramethylene glycol
dispersions
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP02730221A
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German (de)
English (en)
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EP1387859A1 (fr
Inventor
Detlev-Ingo SCHÜTZE
Gerald Kurek
Thorsten Rische
Jürgen Urban
Tillmann Hassel
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Covestro Deutschland AG
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Bayer MaterialScience AG
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/04—Processes in which the treating agent is applied in the form of a foam
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3821—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
    • C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
    • C08G18/3872—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfoxide or sulfone group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C11/00—Surface finishing of leather
    • C14C11/003—Surface finishing of leather using macromolecular compounds
    • C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C08G2150/60—Compositions for foaming; Foamed or intumescent coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2290/00—Compositions for creating anti-fogging
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Definitions

  • the invention relates to novel aqueous polyurethane-polyurea dispersions based on polycarbonate polyols and polytetramethylene glycol polyols, a process for their preparation and their use as coating compositions, in particular for flexible substrates such as textile and leather.
  • PUR dispersions Polyurethane-polyurea dispersions, hereinafter referred to as PUR dispersions, are now used in an increasing number of fields, and the resulting coatings must accordingly fulfill very different requirement profiles.
  • properties such as the achievement of high runs in one line or the production of stable foams are also desirable. This can streamline the processing steps in the overall coating process and reduce associated production costs.
  • properties such as high resistance to hydrolysis with high kinking, scratching and abrasion resistance should be fulfilled.
  • the object of the present invention was therefore to provide alternative PUR dispersions as coating compositions for flexible substrates, which meet the requirements of the PUR dispersions of the prior art, but at the same time have the aforementioned properties.
  • ionically and / or nonionically hydrophilicized, aqueous PU dispersions based on polycarbonate polyols and polytetramethylene glycol polyols make it possible to produce coatings on substrates having the aforementioned property profile.
  • the coatings according to the invention have improved foamability, high abrasion resistance and extremely high scratch, kink and hydrolysis resistance.
  • the PU dispersions according to the invention preferably have an ionic and nonionic hydrophilization.
  • a particularly preferred embodiment of the PU dispersions according to the invention is anionically and nonionically hydrophilicized.
  • Suitable diisocyanates (A1) are generally those of the molecular weight range 140 to 400 having aliphatically, cycloaliphatically, araliphatically and / or aromatically bound isocyanate groups, such as e.g. 1,4-diisocyanatobutane, 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- and 2,4,4 respectively Trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4-bis- (isocyanatomethyl) -cyclohexane, 1-isocyanato-3,3 , 5-trimethyl-5-isocyanatomethylcyclohexane (isophorone di
  • A1 are polyisocyanates or polyisocyanate mixtures of the type mentioned with exclusively aliphatically and / or cycloaliphatically bonded isocyanate groups.
  • Very particularly preferred starting components (A1) are polyisocyanates or polyisocyanate mixtures based on HDI, IPDI and / or 4,4'-diisocyanatodicyclohexylmethane.
  • polyisocyanates (A1) are any polyisocyanates prepared from at least two diisocyanates and prepared by modifying simple aliphatic, cycloaliphatic, araliphatic and / or aromatic diisocyanates with uretdione, isocyanurate, urethane, allophanate, biuret, iminooxadiazinedione and or oxadiazinetrione structure, as described, for example, in J. Prakt. Chem. 336 (1994) 185-200 . DE-A-1 670 666 DE-A-1 954 093 . DE-A-2414413 . DE-A-2 452 532 . DE-A-2 641 380 .
  • DE-A-3 700 209 DE-A-3 900 053 and DE-A-3 928 503 or EP-A-0 336 205 .
  • EP-A-0 339 396 and EP-A-0 798 299 are described by way of example.
  • the PU dispersions according to the invention contain as component (A2) a mixture of polycarbonate polyols and polytetramethylene glycol polyols.
  • the proportion of polycarbonate polyols in the mixture is between 20 and 80 wt .-%, the proportion of polytetramethylene glycol polyols is between 80 and 20 wt .-%.
  • the average molecular weight range of the polymeric polyols (A2) is between 400 and 6000.
  • Suitable polymeric polyols (A2) are, for example, polyethers, polycarbonates, polyestercarbonates which have an OH functionality of at least 1.8 to 4.
  • Polyols in an average molecular weight range of 600 to 4000 with an OH functionality of 2 to 3 are preferably used. Particular preference is given to polyols having average molecular weight ranges from 800 to 2500.
  • the polycarbonates having suitable hydroxyl groups are obtainable by reaction of carbonic acid derivatives, for example diphenyl carbonate, dimethyl carbonate or phosgene with diols.
  • diols are ethylene glycol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bis-hydroxymethylcyclohexane, 2 Methyl-1,3-propanediol, 2,2,4-trimethylpentanediol-1,3, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A, tetrabromobisphenol A but also lactone-modified diols in question.
  • the diol component contains from 40 to 100% by weight of hexanediol, preferably 1,6-hexanediol and / or hexanediol derivatives, preferably those which, in addition to terminal OH groups, have ether or ester groups, for example products which are obtained by reacting 1 mol of hexanediol with at least 1 mol, preferably 1 to 2 mol, of caprolactone according to US Pat DE-A 1770245 , or by etherification of hexanediol with itself to di- or trihexylenglycol were obtained.
  • the preparation of such derivatives is for example from the DE-A 15 70 540 known. Also in the DE-A 3717060 described polyether-polycarbonate can be used.
  • the hydroxyl polycarbonates should be substantially linear. However, they may optionally be easily branched by the incorporation of polyfunctional components, especially low molecular weight polyols.
  • polyfunctional components especially low molecular weight polyols.
  • glycerol, trimethylolpropane, hexanetriol-1,2,6, butanetriol-1,2,4, trimethylolpropane, pentaerythritol, quinitol, mannitol, and sorbitol, methylglycoside, 1,3,4,6-dianhydrohexitols are suitable for this purpose.
  • Suitable polyether polyols are the polytetramethylene glycol polyethers known per se in polyurethane chemistry, for example via polymerization of tetrahydrofuran by cationic ring opening, such as, for example, in US Pat DE-A 741 476 described, can be produced.
  • monoalcohols (A3) are aliphatic monoalcohols having 1 to 18 C atoms, such as e.g. Ethanol, n-butanol, ethylene glycol monobutyl ether, 2-ethylhexanol, 1-octanol, 1-dodecanol, or 1-hexadecanol.
  • Preferred monoamines (A3) are aliphatic monoamines, e.g. Diethylamine, dibutylamine, ethanolamine, N-methylethanolamine or N, N-diethanolamine.
  • the polyols, aminopolyols or aliphatic, cycloaliphatic and araliphatic polyamines (A4) containing in the PU dispersions according to the invention have a molecular weight below 400 and can be used as a chain extender.
  • Components (A3) or (A4) which contain an ionic group or are capable of forming an ionic group for example dihydroxycarboxylic acids, diaminocarboxylic acids, dihydroxysulfonic acids and diaminosulfonic acids and their salts, such as dimethylolpropionic acid, hydroxypivalic acid, 2- (2-aminoethylamino) ethanesulfonic acid, ethylenediamine-propyl- or butylsulfonic acid, 1,2- or 1,3-propylenediamine- ⁇ -ethylsulfonic acid, lysine, 3,5-diaminobenzoic acid and their alkali metal and / or ammonium salts; the adduct of sodium bisulfite with butene-2-diol-1,4, polyethersulfonate, the propoxylated adduct of 2-butenediol and NaHSO 3 ( DE-A 24 46 440 ) as well as building blocks
  • PUR dispersions according to the invention contain one or more of the compounds (A3) and / or (A4) which have an ionic group or are capable of forming an ionic group.
  • Preferred stabilizers are sterically hindered phenols (phenolic antioxidants) and / or hindered amines based on 2,2,6,6-tetramethylene piperidine (Hindered Amine Light Stabilizers, HALS light stabilizers).
  • Irganox ® 1010 (Ciba Specialty GmbH, Lampertheim, DE) and / or Tinuvin ® 765 (Ciba Specialty GmbH, Lampertheim, DE).
  • all adjuvants and additives known for PU dispersions such as, for example, emulsifiers, defoamers, thickeners, can be present in the PU dispersions according to the invention.
  • fillers, plasticizers, pigments, carbon blacks and silica sols, aluminum, clay, asbestos dispersions can also be incorporated into the PU dispersions according to the invention.
  • the solids content of the PU dispersions according to the invention is between 10 and 70%. Preferably, they have a solids content of 35 to 70% and more preferably from 50 to 60%.
  • the invention further provides a process for the preparation of the ionically and / or nonionically hydrophilicized, aqueous PU dispersions according to the invention, which comprises first reacting the components A1 and A2 and optionally the components A3 to A6 to form a polyurethane prepolymer, then the polyurethane prepolymer in or is dispersed by addition of water and then optionally reacted with A3 to A6.
  • aqueous polyurethane dispersions can be prepared by methods of the prior art (eg Houben-Weyl, extension and following volumes to the 4th edition, volume E20, H. Bartl and J. Falb, Stuttgart, New York, Thieme 1987, pp. 1659-1693 or D. Dieterich, Prog. Org. Coatings 9, 281 (1981 )) respectively.
  • the NCO / OH ratio in the preparation of the prepolymer is between 1.2-2.8 / 1, preferably between 1.4-2.5 / 1, more preferably 1.6-2.3 / 1 and most preferably between 1.7-2.2 / 1.
  • the components A1 and A2 and optionally the components A3 to A6 are reacted to give a PUR dispersion, optionally with the aid of an organic solvent.
  • Suitable solvents are the conventional lacquer solvents known per se, such as, for example, ethyl acetate, butyl acetate, 1-methoxypropyl-2-acetate, 3-methoxy-n-butyl acetate, acetone, 2-butanone, 4-methyl-2-pentanone, cyclohexanone, toluene , Xylene, chlorobenzene or white spirit.
  • solvents are, for example, carbonic acid esters, such as dimethyl carbonate, diethyl carbonate, 1,2-ethylene carbonate and 1,2-propylene carbonate, lactones, such as ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -methylcaprolactone, propylene glycol diacetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl and butyl ether acetate, N-methylpyrrolidone and N-methylcaprolactam, or any mixtures of such solvents.
  • carbonic acid esters such as dimethyl carbonate, diethyl carbonate, 1,2-ethylene carbonate and 1,2-propylene carbonate
  • lactones such as ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -methylcaprolactone
  • propylene glycol diacetate diethylene glycol dimethyl ether
  • groups capable of neutralization are then converted into the salt form and the dispersion is produced with water.
  • the dispersion can be adjusted very finely divided, so that it has practically the appearance of a solution. But there are also very coarse-part settings possible, which are also sufficiently stable.
  • the optionally used solvent can be removed by distillation after the dispersion.
  • any of the polyurethane dispersions of the invention may be prepared by any of the methods known in the art, such as emulsifier shear, acetone, prepolymer, melt, emulsify, ketimine, and solid spontaneous dispersion, or derivatives thereof be used.
  • emulsifier shear emulsifier shear
  • acetone acetone
  • prepolymer emulsifier shear
  • melt emulsify
  • ketimine ketimine
  • solid spontaneous dispersion or derivatives thereof be used.
  • a summary of these methods can be found in methods of organic chemistry ( Houben-Weyl, extended and following volumes to the 4th edition, volume E20, H. Bartl and J. Falbe, Stuttgart, New York, Thieme 1987, pp. 1671-1682 ).
  • Preference is given to the melt emulsification and the acetone process.
  • Particularly preferred is the acetone process.
  • Excess isocyanate groups are reacted by reaction with polyfunctional isocyanate-reactive compounds (chain extension).
  • chain extension preference is given to water or the polyamines already mentioned under (A4), especially preferably di- and triamines, hydrazine and the sodium salt of 2- (2-amino-ethylamino) -ethanesulfonklare used.
  • A3 monoamine or monoalcohol
  • diethylamine, dibutylamine, ethanolamine, N-methylethanolamine or N, N-diethanolamine is possible.
  • the PU dispersions of the invention by polyacrylates.
  • an emulsion polymerization of olefinically unsaturated monomers for example esters of (meth) acrylic acid and alcohols having 1 to 18 carbon atoms, styrene, vinyl esters or butadiene, as described, for example, in US Pat DE-A-1 953 348 .
  • EP-A-0 189 945 and EP-A-0 308 115 is described.
  • the monomers contain one or more olefinic double bonds.
  • the monomers may contain functional groups such as hydroxyl, epoxy, methylol or acetoacetoxy groups.
  • Another object of the present invention is the use of the hydrophilic aqueous polyurethane dispersions according to the invention as a coating agent for the preparation of coated substrates.
  • the invention also relates to coating compositions containing the PU dispersions of the invention.
  • the polyurethane dispersions according to the invention are used either alone or in combination with other aqueous binders.
  • aqueous binders may be composed, for example, of polyester, polyacrylate, polyepoxide or polyurethane polymers.
  • the combination with radiation-curable binders, such as in the EP-A-0 753 531 are described is possible.
  • the PU dispersions of the invention are stable, storable and ready for shipping and can be processed at any later time.
  • coatings with different properties are obtained. So soft sticky layers, thermoplastic and rubber-elastic products of different degrees of hardness can be obtained up to glass hard thermosets.
  • the hydrophilicity of the products may also vary within certain limits.
  • the elastic products can be processed at higher temperatures, for example 100 to 180 ° C, thermoplastic, unless they are chemically crosslinked.
  • compounds containing oligomeric polysiloxane segments having at least two isocyanate-reactive groups having molecular weights of from 300 to 6000, preferably from 500 to 1500 can be added to the aqueous PU dispersions according to the invention.
  • These compounds have, for example, structural units -O-Si (R) 2 -, where R is a C 1 -C 4 -alkyl or a phenyl radical.
  • auxiliaries and additives of textile coating technology such as, for example, pigments, leveling agents, UV stabilizers, antioxidants, fillers, plasticizers, carbon blacks and silica sols, aluminum, clay, asbestos dispersions or thixotropic agents, can be admixed with the PU dispersions according to the invention , In this way, ready-to-use aqueous coating compositions which are virtually unlimited shelf life at room temperature and cure at relatively low temperatures of 120 to 150 ° C within 2 to 3 minutes to coatings with in particular very good wet adhesion.
  • the coating compositions according to the invention may be present in the end product.
  • up to 70%, based on the total dry substance, of such fillers may be present in the end product.
  • the PUR dispersions according to the invention are particularly suitable for applications in the field of upholstered furniture, occupational safety and automobile interiors because of their excellent foamability, good abrasion resistance, scratch, kink and hydrolysis resistance, as well as for producing very stable high foam coverings just a dash, which otherwise can only be achieved with high-solids coatings.
  • the invention thus relates to the use of the polyurethane dispersions of the invention in the field of upholstered furniture, occupational safety and car interior equipment and for the production of high foam pads in one stroke.
  • the invention likewise relates to coated substrates comprising a substrate which has on one side a coating containing the PU dispersions according to the invention.
  • Suitable substrates are, for example, woven and non-woven textiles, leather, paper, hardboard, straw, paper-like materials, wood, glass, plastics of various kinds, ceramics, stone, concrete, bitumen, porcelain, metals or glass fibers.
  • Preferred substrates are flexible substrates, particularly preferred are textiles and leather.
  • the PU dispersions of the invention or the pastes produced therefrom as coating compositions are applied to a porous base, which then remains connected to the finished product, such as woven or non-woven textiles or fiber mats, felts or nonwovens, paper webs, foam films or Split leather, which causes an immediate solidification of the coating due to their suction effect. It is then dried at elevated temperature and optionally compressed. The drying can also be done on smooth porous or nonporous materials, such as glass, paper, cardboard, ceramic materials, metal, silicone rubber, aluminum foil. Subsequently, the finished sheet is lifted and used as such or is applied by the reversal process by gluing, Flammkaschieren, calendering on a substrate.
  • the PU dispersions of the invention can perform different functions, e.g. an antistatic and wrinkle-free finish, as a binder for nonwovens, as adhesives, adhesion promoters, laminating agents, water repellents, plasticizers, binders, as auxiliaries in the printing and in the paper industry, as an additive to polymers, as sizing agents, for example for glass fibers and leather equipment.
  • the application of the coating composition according to the invention can be carried out by direct brushing onto the substrate with the aid of doctor blades, rollers or wire knives. As a rule, several layers are applied in succession, but preferably two. The subsequently applied topcoat protects the entire composite against mechanical stress and abrasion.
  • the application of the coating composite of base and top coat is also possible by the so-called reversal process.
  • the top coat is first applied to a release liner and dried. After applying a second primer or adhesive coating, the textile substrate is slightly pressed into the still moist layer. After drying, a solid composite of coating and substrate is formed, which is detached from the release carrier and in its structure largely corresponds to the direct coating described above.
  • the drying of the products obtained by various application techniques can be carried out at room temperature or at elevated temperature.
  • the drying temperature to be chosen on a case by case basis, apart from the chemical composition of the material, in particular the moisture content, the drying time and the drying time Layer thickness is determined easily by a pre-test. For a given heating time, the drying temperature must always be below the solidification temperature.
  • the fabrics can be coated with a finish to increase the resistance of their surface.
  • aqueous dispersions or solutions are preferably used for this purpose.
  • a release paper is inserted in front of the rear roller.
  • a feeler gauge adjusts the distance between the paper and the front roller. This distance corresponds to the film thickness (wet) of the resulting coating, and can be adjusted to the desired run of each stroke.
  • the coating is also possible consecutively in several strokes.
  • the products aqueous formulations are previously made by addition of ammonia / polyacrylic acid to a viscosity of 4500 mPa s
  • the release paper is pulled vertically downwards, taking on the paper the corresponding film is created. If several strokes are applied, each individual stroke is dried and the paper is inserted again.
  • the determination of the average particle sizes (indicated by the number average) of the PUR dispersions was carried out by means of laser correlation spectroscopy (device: Malvern Zetasizer 1000, Malver Inst. Limited).
  • the stated viscosities are flow times, measured in accordance with DIN 53 211 in the DIN cup 4 mm.
  • Part 1 203.3 g Diol III 156.0 g Diol IV 77.0 g Diol I 14.6 g EOX polyether Part 2: 48.9 g Hexane-1,6-diol 64.6 g isophorone Part 3: 1016.5 g acetone Part 4: 34.7 g isophoronediamine 6.9 g diaminosulphonate 2.2 g hydrazine hydrate 134.4 g water Part 5: 298.1 g water
  • the result is a dispersion having a solids content of 60.4% and an outlet viscosity at 23 ° C (4 mm cup AFAM 2008 / 1050304-00 D) of 27 s.
  • Part 1 400.0 g Diol IV 260.0 g Diol III 27.0 g EOX polyether 8.6 g dimethylolpropionic Part 2: 121.0 g Hexane-1,6-diol Part 3: 1451.7 g acetone Part 4: 5.2 g 1,2 diaminoethane 3.0 g hydrazine hydrate 24.0 g Diaminocarboxylat 141.8 g water Part 5: 1091.9 g water
  • the result is a dispersion having a solids content of 41.0% and an outlet viscosity at 23 ° C (4 mm cup AFAM 2008 / 1050304-00 D) of 20 s.
  • Part 1 311.7 g Diol II 88.0 g Diol IV 12.4 g EOX polyether Part 2: 41.4 g Hexane-1,6-diol 54.7 g isophorone Part 3: 903.5 g acetone Part 4: 30.2 g isophoronediamine 5.22 g diaminosulphonate 0.75 g hydrazine hydrate 137.8 g water Part 5: 249.5 g water
  • the result is a dispersion having a solids content of 59.5% and an outlet viscosity at 23 ° C (4 mm cup AFAM 2008 / 1050304-00 D) of 29 s.
  • the result is a dispersion having a solids content of 40.4% and an outlet viscosity at 23 ° C (4 mm cup AFAM 2008 / 1050304-00 D) of 15 s.
  • Part 1 30.0 g Diol III 200.0 g Diol IV 13.5 g EOX polyether 4.3 g dimethylolpropionic Part 2: 60.5 g Hexane-1,6-diol Part 3: 725.9 g acetone Part 4: 2.6 g 1,2-ethylenediamine 25.2 g Hydrophilic 1.50 g hydrazine hydrate 2.50 g dimethylethanolamine 109.6 g water Part 5: 505.0 g water
  • the result is a dispersion having a solids content of 40.0% and an outlet viscosity at 23 ° C (4 mm cup AFAM 2008 / 1050304-00 D) of 19 s.
  • Part 1 340.0 g Diol I 320.0 g Diol IV 27.0 g EOX polyether 8.6 g dimethylolpropionic Part 2: 149.6 g Hexane-1,6-diol Part 3: 1502.6 g acetone Part 4: 4.9 g 1,2-ethylenediamine 53.6 g Hydrophilic 3.0 g hydrazine hydrate 5.3 g dimethylethanolamine 220.8 g water Part 5: 1049.1 g water
  • the result is a dispersion having a solids content of 40.3% and an outlet viscosity at 23 ° C (4 mm cup AFAM 2008 / 1050304-00 D) of 16 s.
  • Part 1 250.0 g Diol III 80.0 g Diol V 13.5 g EOX polyether 4.3 g dimethylolpropionic Part 2: 67.2 g Hexane-1,6-diol Part 3: 737.8 g acetone Part 4: 4.5 g 1,2-ethylenediamine 13.1 g diaminosulphonate 2.65 g hydrazine hydrate 130.9 g water Part 5: 501.6 g water
  • the result is a dispersion having a solids content of 40.9% and an outlet viscosity at 23 ° C (4 mm cup AFAM 2008 / 1050304-00 D) of 17 s.
  • Part 1 250.0 g Diol III 22.0 g Diol VI 13.5 g EOX polyether 4.3 g dimethylolpropionic Part 2: 60.5 g Hexane-1,6-diol Part 3: 622.8 g acetone Part 4: 2.6 g 1,2-ethylenediamine 13.0 g diaminosulphonate 1.50 g hydrazine hydrate 87.5 g water Part 5: 444.4 g water
  • the result is a dispersion having a solids content of 39.0% and an outlet viscosity at 23 ° C (4 mm cup AFAM 2008 / 1050304-00 D) of 15 s.
  • the PU dispersions of Examples 1-6 according to the invention show significantly better hydrophilicity than the PUR dispersions of the prior art (PUR I / II) and Comparative Examples 7 and 8.
  • the production of the blown foam is carried out with commercial foam aggregates, e.g. Hansa mix.
  • Foaming pastes prepared according to this procedure from Example 1 can be spread in one stroke to give foams having a layer thickness of at least 2.0-2.5 mm, that is to say solid deposits of almost 800 g / m 2 and more, depending on the effectiveness of the drying aggregate.
  • Foams of PUR II produced under similar conditions reach foam deposits of about 200-250 g / m 2 , ie layer thicknesses of 0.6-0.8 mm. Higher runs lead to deep cracks in the foam surface.
  • the foam made from the PUR dispersion of Example 1 has significantly better scratch and abrasion resistance than the foams of the prior art conventional PUR dispersions (PUR II and III).
  • Formulation of an aliphatic diamine with auxiliaries and additives in butanone 400 g of the formulation correspond to 1 Val NH 2 .
  • Tl binder 4 There is a mixture of 1000 Tl binder 4; 40 parts of carbon black preparation (b); 15 T1 siloxane (s) and 80 ⁇ l thickener (c) produced. This mixture is doctored onto the dried topcoat so that a solids deposit of 45 g per square meter results (knife gap 0.12 mm). The intermediate line is dried according to the top coat.
  • cover and intermediate coat separator is obtained.
  • the coating is now glued with split leather in two different ways. After bonding, the release paper is peeled off and the resulting coated leathers are evaluated and tested for physical fastness.
  • Tl mixture 5 50 T1 crosslinker (a) and 60 Tl thickener (c) produced.
  • This mixture is doctored onto the top and intermediate release paper to give a 50 g per square meter pad (knife gap 0.18 mm).
  • the glue line is only gently dried with a temperature program of 80 - 105 ° C so that it still sticky comes out of the drying channel.
  • a split leather is placed on this glue line and pressed with a moderate pressure roller. After 15 minutes, the release paper is peeled off (leather A).
  • a mixture of prepolymer C and hardener D with a mixing ratio of 1000: 318 is sprayed onto the release liner provided with cover and intermediate coat in a technical two-component injection-molding line in such a way that a solids deposit of 100 g per square meter results.
  • a split leather is placed in the reacting mass and pressed with a moderate pressure roller. Thereafter, it is dried for 5 min at 80 ° C and the release paper subtracted (leather B).
  • Both leather A and leather B were characterized by a strong fullness and coverage of the coating. They were both extremely tight.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Claims (14)

  1. Dispersions de PUR aqueuses, ioniquement et non ioniquement hydrophilisées contenant
    A1. des polyisocyanates,
    A2. un mélange de polycarbonate- et de polytétraméthylèneglycolpolyols,
    A3. éventuellement des monoalcools ou des monoamines,
    A4. des polyols, des aminopolyols ou des polyamines qui disposent de groupes carboxy ou carboxylate et/ou sulfonate,
    A5. éventuellement un polyoxyalkylèneéther avec au moins un groupe hydroxy ou amino,
    A6. éventuellement des antioxydants et/ou des agents de protection à la lumière et/ou d'autres auxiliaires et additifs.
  2. Dispersions de PUR selon la revendication 1 contenant
    A1. de 5 à 30 % en poids de polyisocyanates,
    A2. de 55 à 87 % en poids d'un mélange de polycarbonate- et de polytétraméthylèneglycolpolyols,
    A3. de 0 à 10 % en poids de monoalcools ou de monoamines,
    A4. de 1 à 20 % en poids de polyols, d'aminopolyols ou de polyamines, qui disposent de groupes carboxy ou carboxylate et/ou sulfonate,
    A5. de 0 à 10 % en poids d'un polyoxyalkylèneéther avec au moins un groupe hydroxy ou amino, et
    A6. de 0 à 10 % en poids d'antioxydants et/ou d'agents de protection à la lumière et/ou d'autres auxiliaires et additifs, la somme des pourcents en poids des constituants A1 à A6 étant égale à 100 %.
  3. Dispersions de PUR selon la revendication 1 contenant
    A1. de 10 à 25 % en poids de polyisocyanates,
    A2. de 60 à 85 % en poids d'un mélange de polycarbonate- et de polytétraméthylèneglycolpolyols,
    A3. de 0 à 10 % en poids de monoalcools ou de monoamines,
    A4. de 1 à 15 % en poids de polyols, d'aminopolyols ou de polyamines, qui disposent de groupes carboxy ou carboxylate et/ou sulfonate,
    A5. de 1 à 10 % en poids d'un polyoxyalkylèneéther avec au moins un groupe hydroxy ou amino, et
    A6. de 0,5 à 8 % en poids d'antioxydants et/ou d'agents de protection à la lumière et/ou d'autres auxiliaires et additifs, la somme des pourcents en poids des constituants A1 à A6 étant égale à 100 %.
  4. Dispersions de PUR selon la revendication 1 contenant
    A1. de 13 à 20 % en poids de polyisocyanates,
    A2. de 70 à 82 % en poids d'un mélange de polycarbonate- et de polytétraméthylèneglycolpolyols,
    A3. de 0 à 10 % en poids de monoalcools ou de monoamines, A4. de 1 à 10 % en poids de polyols, d'aminopolyols ou de polyamines, qui disposent de groupes carboxy ou carboxylate et/ou sulfonate,
    A5. de 1 à 5 % en poids de polyoxyalkylèneéther avec au moins un groupe hydroxy ou amino, et
    A6. de 1 à 6 % en poids d'antioxydants et/ou d'agents de protection à la lumière et/ou d'autres auxiliaires et additifs, la somme des pourcents en poids des constituants A1 à A6 étant égale à 100 %.
  5. Dispersions de PUR selon la revendication 1, caractérisées en ce que la part des polycarbonatepolyols dans le mélange A2 est de 20 à 80 % en poids, la part des polytétraméthylèneglycolpolyols est de 80 à 20 % en poids, la somme des pourcents en poids des polycarbonate- et polytétraméthylèneglycolpolyols étant égale à 100 %.
  6. Dispersions de PUR selon la revendication 5, caractérisées en ce que la part des polycarbonatepolyols dans le mélange A2 est de 25 à 70 % en poids, la part des polytétraméthylèneglycolpolyols est de 30 à 75 % en poids, la somme des pourcents en poids des polycarbonate- et polytétraméthylèneglycolpolyols étant égale à 100 %.
  7. Dispersions de PUR selon la revendication 5, caractérisées en ce que la part des polycarbonatepolyols dans le mélange A2 est de 30 à 65 % en poids, la part en polytétraméthylèneglycolpolyols est de 35 à 70 % en poids, la somme des pourcents en poids des polycarbonate- et polytétraméthylèneglycolpolyols étant égale à 100 %.
  8. Procédé pour la préparation des dispersions de PUR selon la revendication 1, caractérisé en ce que l'on fait réagir dans un premier temps les constituants A1 et A2 ainsi qu'éventuellement les constituants A3 à A6 en un prépolymère de polyuréthane, en ce que l'on disperse alors le prépolymère de polyuréthane dans de l'eau ou par addition d'eau et en ce que l'on fait ensuite réagir éventuellement avec de A3 à A6.
  9. Utilisation des dispersions de PUR selon la revendication 1 comme agents de revêtement pour la préparation de substrats revêtus.
  10. Utilisation des dispersions de PUR selon la revendication 9, caractérisée en ce que le substrat est un textile ou du cuir.
  11. Utilisation des dispersions de PUR selon la revendication 1 dans le domaine des meubles rembourrés, de la protection au travail et de l'équipement intérieur de véhicules automobiles.
  12. Utilisation des dispersions de PUR selon la revendication 1 pour la préparation de hautes couches de mousse en seulement une application.
  13. Substrats revêtus contenant un substrat qui présente sur un côté un revêtement contenant des dispersions de PUR selon la revendication 1.
  14. Agent de revêtement contenant les dispersions de PUR selon la revendication 1.
EP02730221A 2001-05-09 2002-04-29 Dispersions de polyurethanne-polyuree utilisees comme agent d'enduction Expired - Lifetime EP1387859B1 (fr)

Applications Claiming Priority (3)

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DE10122444A DE10122444A1 (de) 2001-05-09 2001-05-09 Polyurethan-Polyharnstoff Dispersionen als Beschichtungsmittel
DE10122444 2001-05-09
PCT/EP2002/004702 WO2002090413A1 (fr) 2001-05-09 2002-04-29 Dispersions de polyurethanne-polyuree utilisees comme agent d'enduction

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HK1068906A1 (zh) 2005-05-06
CA2446280C (fr) 2010-03-30
CA2446280A1 (fr) 2002-11-14
KR20040029973A (ko) 2004-04-08
ATE474007T1 (de) 2010-07-15
CN1524098A (zh) 2004-08-25
CN100467510C (zh) 2009-03-11
DE10122444A1 (de) 2002-11-14
TWI293962B (en) 2008-03-01
MXPA03010118A (es) 2004-03-19
US20030105219A1 (en) 2003-06-05
WO2002090413A1 (fr) 2002-11-14
EP1387859A1 (fr) 2004-02-11
US6642303B2 (en) 2003-11-04
JP2008248250A (ja) 2008-10-16
JP2004534119A (ja) 2004-11-11
BR0209529A (pt) 2004-03-09
DE50214533D1 (de) 2010-08-26
ES2347138T3 (es) 2010-10-26

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